Process of making iodin products.



JOSEF HERTKORN, OF BERLIN, GERMANY PROCESS OF MAKING- IODIN PRODUCTS.

Specification of Letters Patent.

' Ifatented Oct. 20, 1908.

Application filed June 1,1908. Serial No. 435,890. (Spechnenm) To all :whom it ma concern:

Be it known t at I, Josnr HERTKORN, doctor of philosophy, chemist, and resident of Berlin, Germany, Paulstrasse 8, have invented a new and useful Im roved Process of Making Iodin Products, 0 which the following is a specification. My invention relates to a rocess of making iodin products, and especially those which can be used as a substitute for iodoform.

Iodoform, which is much used in surgery and therapeutics, causes considerable irritation when used on open wounds, and has the additional disadvantage of possessing a very substances leave little or no stain on the skin,

their color being substantially the reddish brown or bright yellowish brown of the cicatrix of a wound. On the other hand, they possess excellent and permanent antiseptic roperties and are at the same time nonirritant and odorless. Accordin to my invention, these substances are 0 tained by treatin the products of condensation of aldehy es with ketones and their derivatives of both the aliphatic and aromatic series,

duct is almost entire with iodin orcompounds which yield iodin. These substances, therefore, combine the antiseptic property of iodoform with the properties of the'unstable. aldehyde compounds and of iodin.

The iodized product of condensation of acetone and formaldehyde may be re arded as the chief re resentative of the i0 oform substitutes of t 1e aliphatic series. This proy insoluble in water, is solublein alcohol, ether and amyl-acetate, the resulting liquid being of a yellow color, and is especially soluble in acetone and other ketones, the resulting liquid being then of a dee er yellow color. On the other hand, it

. is a most insoluble in cold benzin, or benzol,

or oil of turpentine, but artiall soluble in hot benzm, or benzol, t e resu ting li uid his rose coloring, however, does not arise from bined iodin, in the presence of heat.

. smell of iodoform and by the products when heate an actual solution of the substance, but from a partial segregation of theunstably c q rlrlie solutions of this product in alcohol or acetone, when soda or an alkali are added and the whole heated, are characterized by a recipitation of iodoform, the liquid then losing its color. The iodin in these roducts is introduced partly as a substitution product and partly as an addition product, according to. the method ado ted and the particular reagents used. v If t e iodin is added to an acid or neutral liquid addition products are mainly formed. If the iodin is added to an alkaline solution, substitution products reponderate. The former products when t ey are dried are reddish brown in color, and of a compact and horny nature, while the latter are yellow or yellowish brown in color and softer. The iodin addition products liberate iodin at normal tem eratures, and these (i remain ulverulent and are onl carbonized at a big tem erature. The iodin substitution products, ow-

ever, become softened by heat, and when heated on a platinum foil or in a retort give ofl astrong odor of iodin and formaldehyde. The hysical, chemical, and antiseptic properties of the iodized condensation products formed from the higher aldehydes and ketones or their derivatives of both the aliphatic and aromatic series are in general identical with or very similar to those of the lower aldehydes and ketones. A condensation product as normally roduced, still contains a large percentage 0 uncondensed aldehyde, as much as 50 per cent., for example, combined with alcoholic alkali, otash, for example. The more aldehyde t e iodized condensation product contains in a combined form, the lighter is its color and the more iodin it contains. The amount of iodin contained in these products varies from 15 to 46 per cent, according to the methods and reagents used; The absorption of iodin is at its lowest limit in an acid liquid, and at its hi hest limit inan alkaline li uid.

hecondensation of the aldehydes with the ketones or their derivatives may, for the bonates, or other salts ha a condensing action on such com ounds. hesec'ondensationproducts areelthercolorless or white, or of a yellowish ondeep orange color, according 5 to the nature of the condensing agent and the manner of using it. v

Instead of the simple lower or higher aldehydes and ketones, the polymerized or condensed aldehydes' or' keto'nes may be used, as may also the substitution products, oxyaldehydes, ketonio alcohols and the like. amples of these are trioxymethylene, paraldehyde, metaldehyde', avdol, croton-aldeh de, chloral, salicyl-aldehyde, 'cinnammic a dehyde and the like, or mesityl-oxid,

phorone, chlor acetone, anthraquinone, benzo%lcarbinol and thelike.

or iodizing the condensation products, the iodin maybe used either in the form of a powder or in solution. In the former case, the iodin is stirred up in an alkaline, neutral, or acid liquid. In the latter case, an alcoholic or iodin-hydrocarbon solution may be used. Still other ways are a solution of iodin in iodid of potash, iodin in iodic acid, iodin in hydrio'dlcacid or the like. Other iodin-yielding substances either with or without the additionofan alkali or a carbonate or bicarbonate, may. also be used. Thecondensation and iodization may be advantageously carried out in one operation. Exam le '1. A mixture is made of 100 grams 0' acetone or some other ketone with about 250 grams of 40 per cent. of formalde- 3 h de in from one-half to 2 liters of water. 0 this mixture is then added from 30 to 60 rams of soda lye, and the mixture is gently sated until spontaneous heating sets in, and the liquid assumes a yellow color. The liq- 40 uid is then cooled, whereupon condensation takes place, and is left to stand for from one to two days, being frequently stirred or shaken. In this way, an orange ellow, flocculent precipitate is formed. if the temperature rises higher, compact, orangered lumps are formed, which even when heated to 21. hi her degree of heat do not soften, and whic when iodization is effected, yield an iodin addition product which is of a horny and-compact nature. The mixture is then heated to'from 40 to 50 C. and the heating is continued until the yellow recipitate has been com letely de osited. he liquid is then allowe to stand and cool ofl for a considerable time. The preci itate is then separated from the li uid, pu verized, V

and thoroughl washed with water. The

' air-dried or st' 1 moist and finely powdered condensation product is covered with a layer of light benzin, and to it is added from onehalf to an equal quantity of iodin and the mass is warmed for from 12 to 24 hours at a temperature of about 40 to 60 C. on a water bath under a reflux condenser.

the reaction may be aided if an equal weight Sometimes 1 or half of the weight of the iodin, of powdered crystalline soda or potash, or bicarbonate be radually 1 added, until eflervescence no FOnger takes place. Should the quantity of iodm prove too small, additional iodin is added until the benzin is permanently 001- 1 ored red. The reddish brown precipitate is washed with benzin and water, and then dried either in the air or at a tem eratur e of from 30 to 40 C. and pulverize It contains about 28 per cent. of iodin.

Example 2. The liquid and precipitate ob tained' according to Example 1, before the addition of the benzin, is treated withcarbon dioxid up to the point of saturation for the purpose of neutralizing the lye or for the same urpose, the mixed product is first subjecte to a current of warm air and from 80 to 100 grams of carbonate of soda orpotash is dissolved in the liquid. 100 grams'of iodin are then gradually stirred into the liquid, which is heated at from 40 to 60 C. on a water bath in a closed vessel under a reflux condenser until the iodin is entirely combined with the precipitate. In order to secure complete saturation with iodin, additional iodin in small amounts is added from time to time until the li uid is permanently colored red, and the who e of the alkali decom osed. The yellowish brown precipitate is 1 tered oil, washed with cold water until it is free from alkali, dried at a temperature of from 20 to 30 C. and the product pulverized to a fine flour. Thedatter contains about 40 per cent. of iodin. I

Example 3. 1000 grams of dry, very finely powdered white condensat1on product 'formed by treating acetone and formaldehyde with soda as m Example 1, are stirred into three liters of water, and mixed with 1000 ams of iodin in the form of a concentrate solution of iodin'and potassium iodid, the liquid being frequently stirred meantime. The mass is then heated on a water bath to a temperature of from 40 to 50 C. and powdered bicarbonate of potassium is added in small amounts from time to time, from 500 to 600 grams of this reagent being requlred, and the liquid is maintained at the same temper ature from 2 to 5 hours more, stirring being constantly ke t up. The mass is then allowed to cool d ewn completely. The product is drawn off by suction, washed with cold water, dried at a temperature of from 20 to 30 C. and reduced to a fine powder. TlllS powder contains 30 per cent. of iodin.

Example 4. 30 grams of condensat1on roduct obtained from acetone and formalde yde with alcoholic lye (prepared as in Exam le 1, except that, instead of soda, alcoholic ye is used) are mixed with 7.2 rams of iodin and the whole mass thorough y pulverized, said mass being then mixed with 12 cm of a solution of iodlc acid, one cm of this solution containing 0.20826 grams of H10 in 15 cm of to 50 C. while being production of 50.2

water. The massjs then diluted with 115 cm of water, and heated on a water bath to 45 C.,-afterwhich 16.8 grams of iod'n and 28 om of iodic acid are added, and t e mass kept for 30 hours at a tem rature of from 45 I equently shaken. The i. precipitate is removed by suction "and waslied and dried in the air, resulting in the ams of a reddish brown iodin product, smel strongly of iodin and contamin 36.03 per cent. of iodin. In this method, t e'hydriodic acid set freein the substitution reaction may at once be converted into iodin and water under the action of the iodic acid, a calculated amount of which is added. As, however, besides the substitution, an addition of iodin also takes lace, theiodin being in this reaction remove without the formation of hydriodic acid, the liquid becomes sliglitl acidowing. to the presence of .f'ree iodic aci reaction takes place according to the following equations:

drawn off, washed, and dried as usual, and

contains 29 grams. It is deep brown in color and has a slight smell of iodin, and contains 24.58 per cent. of iodin.

Example 6. 20 grams of condensation product obtained as in Example 1 are pulverized with 100 cm mixture is then heated on a water bath for 10 hours at a temperature-of from 45 to 50 (1, be' shaken frequently; The mass is then coo ed down, the'preclpitate removed, washed, and dried at ordinal; temperatures, the result being 29 grams 0 brown colored iodin product containing 25.7. per cent. of iodin. There is no loss of iodin m these .ex-' .amples, as the whole is recovered in the washing liquors. 7

Example 7. A reddish brown iodin product containing 45.6 per cent; of iodin ma be obtained frombenzylidene-aceton'e and enzaldehyde, when condensed and iodized accordingto Example 4. This product is an.

iodized dibenzylidene-acetone.

obtained from phorone and an excess of formaldehyde, and condensed with aqueous soda lye according to Example 1,'and iodized according to Example 3.

1 obtained from obtained from mesit with a slight odor, may

temperature of i uid.

of hydriodic acid and mixed with 22.1 cm of iodic acid. -The Example 9. A reddish brown iodin product containing.34.6 per cent. of iodin may be cratonaldehyde and acetone when obtained as in Example: 1 and iodized according to Example 3.

Example 10. A reddish brown iodin prod uct contalmng 32.54 per cent. of iodin may be I oxid and forms xample 1 and iodized hyde, obtained as in as in Example 3.

Example 11. An iodin product contain mg 35 per cent. of iodin, readily fusible and be obtained from benzaldehyde and acetone obtained as in Example 1 and iodized as in Example 4.

Exam' le 12. Acetone and synthesized salicy'l a dehg de obtained as in Example 1, pro uce awhen I iodize as Example 3, product containing 3-5 percent. of iodin. In car I out this process, I have found thatthe iodizing of the' condensation prod- .ucts inclosed vessels, especially if thesevessels are provided with reflux condensers,

IYields a product containing a considerably lgher percentage of iodin than when conducted n open'vessels.

In addition to the accretion the normall obtained condensation product by means o alcoholicalkali', the quantity of iodin absorbed can be still further increased by first completely carrying out the iodization by the substitution method in an alkaline li uid andsubsequently terminatin the same addition method in an acirfliq- 0 effect this result, the iodid of potassium formedis decomdposed with dilute acid and the hydriodic aci that is set free is converted in free, active iodin by the addition of a weak oxidizing medium, such as chlorid of iron, iodic acid, or the like. This method is generally applicable for iodization in a neutral or acid liquid, any hydriodic acid that is formed being decomposed as uickly as it is formed into free 1 and imme iately active iodin. If the iodin, or an hydriodic acid that may be formed be added: instead of the double com ound bein formed, it ma ha pen that no ee h drio ic acid is forme do not limit myse .f to the exact mediums for dissolving and separating iodin above described, as other mediums which will produce the same effect may be used, and smiilarly instead of-the-aldehydes and ketones mentioned above, there may be used all other aldehydes andketones or their derivatives having the same 'or similar properties for the purpose in question. v

1. The herein described process for making products containing iodin, which consists in treating the condensation products of aldehydes and ketones with iodin-yielding substances, substantially as described.

2. The herein described process for obtaining products containing iodin. which of aldehyde to.

consists in condensing a mixture of anfa1de stance, heating the mass; and purifying the hyde and a ketone, and treating the roduct product obtained, substantially as described. with a substance which under heat Wlll yield a In testimony, that I claim the foregoing as iodin, substantially as described. my invention, I have signed my name in 5 3. The herein described process for making products containing iodin, which consists in condensing a mixture of an aldehyde and aketone by means of an alkali, separating the precipitate, warming the same with benzin, 10 and adding thereto an iodin-yielding subay 1908. ,JOSEF HERTKORN.

Witnesses: I

WOLDEMAR HENRY HASPER;

resence of two witnesses, this 19th day-of 

